Triazinylalkyl phosphates



United States Patent 3,102,885 TRIAZINYLALKYL PHOSPHATES Gerald Berkelhammer, Ewing Township, Mercer County, Frank A. Wagner, Jr., Belle Mead, and Richard J. Magee, Princeton, N.J., assignors to American Cyanamid Company, Stamford, Conn a corporation of Maine No Drawing. Filed July 19, 1962, Ser. No. 211,101 7 Claims. (Cl. 260-248) A-C o N in which A is the radical:

wherein R and R are lower alkyl,

Y and Y are each oxygen or sulfur,

R and R are either hydrogen or lower alkyl,

B represents hydrogen, lower alkyl, or lower alkoxy,

D is hydrogen, a lower alkyl radical, a lower alkoxy radical, or the radical represented by A.

Illustrative compounds prepared by the process of the invention are:

0,0-dimethyl S-(4,6-dirnethyl-s-triazin- 2-y1) methyl ester of phosphorodithioic acid 0,0-diethyl S-(4,6-dirnethyl-s-triazin-2-yl)methyl ester of phosphorodithioic acid 0,0'-dimethyl S-1-(4,6-diethyl-s-triazin-2-yl)ethyl ester of phosphorodithioic acid 0,0-dimethyl S-(4,G-dimethoxy-s-triazin-Z-yl)methyl ester of phosphorodithioic acid O,O-dimethyl S-(4,6-diethoxy-s-triazin-2-yl)methyl ester of phosphorodithioic acid 0,0-dimethy1 S-l-'(4,6-dimethyl-s-triaZin-2-yl) ethyl ester of phosphorodithioic acid 0,0,0,O'-.tetrarnethyl 8,5-( 6-methyl-s-triazin-2,4-

diyldimethylene) ester of phosphorodithioic acid 0,0-dimethyl S-(s-triazin-2-yl)methyl ester of phosphorodithioic acid and homologs and isomers thereof.

The compounds of the present invention are prepared in a straightforward manner. This is accomplished by reacting an ammonium or alkali metal salt of a lower dialkylt hiophosphoric acid or lower dialkyldithiophosphoric acid with a haloalkyl substituted triazine in at least equimolar proportions according to the general reaction:

| /0 R0 Y R N N \H H /P SM+ X C-C /CZ RY it "ice wherein: R, R, R R B, D, Y and Y are radicals as above defined, Z is either hydrogen, lower alkyl or the radical:

R2 XC-' R X representing a halogen radical such as chloro, bromo or iodo, and M is an alkali metal, such as sodium, potas-.

sium, lithium or the ammonium radical. However, when Z defined as above is the radical:

it is found that at least two mols of the salt per mol of the s-triazine are required for reaction.

In general, the acid salts include, for example:

Sodium 0,0-dimethyl thiophosphate,

"Potassium O, O -diniethyl dithiophosphate,

Lithium 0,0-dipropyl thiophosphate, Ammonium 0,0-dipropyl dithiophosphate, Lithium O,O-diisopr0py1 thiophosphate, Sodium 0,0-diisopropyl dithiophosphate,

Potassium O-methyl O-ethyl thiophosphate,

Sodium O-rnethyl O-ethyl dithiophosphate, Ammonium O-methyl O-propyl thiophosphate, 1 Potassium O-anethyl O-isopropyl dithiophosphate, Sodium O-methyl S-ethyl dithiophosphate, Potassium O-rnethyl S-methyl dithiophosphate.

Haloalkyl-substituted s-triazine reactants which conform to the general formula:

wherein X, B, Z, R and R are the same as above defined, are illustrated by the following compounds:

2-bromomethyl-4,G-dimethyl-s-triazine, 2-chloromethyl-4,6-dimethyl-s-triazine, 2-ohloromethyl-4,6-dimethoXy-s-triazine, 2-chloromethyl-4,6ediethoxy-s-triazine,

2( l-bromoethyl) -4,6-dipropoxy-s-triazine, 2( l-brornoethyl) -'4, 6-di-n-butoxy-s-triazine, 2( 1 -bromoethyl) 4,6-diethyl-s-triazine,

Q.-( 1-ch1oroethyl-4,6-dimethyl-s-triazine,

2-chloromethy1-s-triazine,

2,4-bis( l-chloroethyl) 6-niethyl-s-triazine, 2-( l-ohioroethyl) -s-triazine,

and an imidate, more fully described in a copending application (for Letters Patent of F. C. Schaefer, Serial No. 12,930, filed on March 7, ,1960'. More specifically, one mole of either l-chloroacetamidine hydrochloride or 1- chloropropionalmidine hydrochloride and three mols of ethyl acetinn'date are reacted to obtain both monoohloroalkyl-s-triazine and a bis(chloroalkyl)-s-triazine and then effecting a separation to recover each s-triazine compound. A third method involves the reaction between 2-diazomethyl 4,6-dichloro-s-triazine and sodium alkoxide, such as sodium methoxide, and further reacting the so-formed product with hydrochloric acid to recover 2- chloromet-hyl-4,6-dialkoxy-s-triazine.

In the preparation of the triazinylalliyl phosphates of the present invention, the amounts of reactants employed will depend upon the product desired. Thus, as mentioned above, usually equimolar quantities are sufiicient. However, at least two mols of the acid salt per mol of the s-triazine are necessary when the s-triazine employed is a bishaloalkyl-substituted striazine.

The reaction is generally'carried out in the presence of an inert organic solvent. Such solvents include, for instance, acetone, methyl isobutyl ketone, alcohol, ether, benzene, chlorinated hydrocarbons and the like. It may be advantageously carried out in the presence of a hydrogen halide acceptor, such as alkali metal carbonates or bicarbonates or alkaline earth carbonate.

, In general, a wide range of temperatures extending from freezing point to'the decomposition temperature of the reaction mixture may be utilized. However, it is found that the reaction may be better carried out at a temperature in a range of 10 C. to 150 C. and preferably from 20 C. to about 100 C.

The new class of compounds of this invention are useful as insecticides, by contact, stomach and systemic action and as acaricides. Such compounds can be used for insecticidal purposes utilizing methods conventionally employed. For example, they may be employed as spray suspensions or dispersions, as dusts by absorption on an inert, finely divided carrier, or as aerosols. Liquid concentrates for dilution with water can also be prepared employing both a compatible organic solvent, such as acetone or xylene, and an emulsifying agent such as a higher aliphatic alcohol, an alkyl aryl sulfonate, or a higher alkyl sulfonate. Solid carrier materials which can advantageously be used, include talc, kaolinite, various clays and similar inert solid diluents. In addition, the new compounds of this invention can be employed as aerosols by dispersing the same into the atmosphere by means of a compressed halogenated hydrocarbon gas such as dichlorodifiuoromethane and equivalents thereof.

The optimum concentration of these compounds to be used with any of the above carriers or methods of application will depend on many factors including the carrier employed, the pest to be controlled, type of surface to be treated, conditions of the application and the particular compound used. In general, however, the compounds of this invention are effective at concentrations of .01% to 1%, based on the total weight of the composition, although as little as 0.0001% or as much as 5%, or even more of the compounds, can be used'with good results.

The following detailed examples are presented as illustrative of the preferred embodiments of the practice of the invention. It is understood that they are not to be taken as limitative thereof.

EXAMPLE 1 0,0-Dl'me'thyl S-(4,6-Dimethyl-s-Triazin-Z-Yl)Mcthyl Ester of Phosphorodithioic Acid In a suitable reaction vessel are dissolved 9.8 parts of potassium -0,0-dirnethyl phosphorodithioate (0.05 mol) 0,0-Di8thyl S-(4,6-Dimethyl-s-Triazine-Z-Yl)Methyl Ester of Phosphorodithioic Acid The procedure of Example 1 is repeated, except that 11.2 parts of potassium 0,0.-diethyl phosphorodithioate (0.05 mol) and 10.1 parts of 2-bromomethyl-4, 6-dimethyl-s-triazine (0.05 mol) are dissolved in 140 parts (by volume) I of anhydrous acetone. A quantitative yield of pale yellow oil is obtained, and after several recrystallizations from petroleum ether, a solid product melting at 180 C.- 19.0" C. is obtained analyzing as:

Calculated: P, 10.08 N, 13.67. Found: P, 10.42; N, 13.35

EXAMPLE 3 0,0-Dimethyl S- (4,6-Diethyl-r-Triazin-Z-Yl)Ethyl Ester of Phosp'horodithioic Acid As in the procedure of Example 1, 2.5 parts of potassium 0,0-diimethyl phosphorodithioate (0.012 mol) and 3.1 parts of 2-(l-bromoethyl)-4,-6-diethyl-s triazine (0.012 mol) are admixed in 65 parts (by volume) of anhydrous acetone. After refluxing for two hours, a 29% yield of product is obtained as a colorless oil analyzing as:

Calculated: P, 9.64; S, 19.95. Found: P, 9.04; S, 20.47. I

EXAMPLE 4 0,0-Dimethyl S-l-*(4,6-Dimethyl-s-Triazin-Z-Yi)Ethyl Ester of Phosphorodithioic Acid 3.9 parts of potassium 0,0-dime-thyl phosphorodithioate (0.02 mol) and 3.4 parts of 4,6-di-methyl-2-(lchloroethyl)-s-triazine (0.02 mol) are dissolved in a total of 65 parts ofmethyl isobutyl ketone. The mixture is heated to C. for seven and one-half hours, cooled to room temperature and the solids filtered off. The filtrate is washed, dried and evaporated to yield 61% of theory of an oil which crystallizes below room temperature.

EXAMPLE 5,

0,0-Dimetlzyl S-(s-Triazin-Z-YDMethyl Ester a Phosphorodithz'oic Acid 9.8 par-ts of potassium 0,0'-dimet-hy1 phosphorodithioate (0.05 mol) and 6.5 parts of 2-chlorornethyl-s-triazine (0.05 mol) in parts (by volume) of anhydrous acetone; are dissolved in a suitable vessel. The mixture is then heated at 50 C. for fifty minutes. The product is obtained in 50% yield as a colorless oil having a refiractive index (11 1.5715.

EXAMPLE 6 0,0-Dimethyl S-(4,6-Dimethyl-s-Triazin-2-Yl) Methyl .Ester of Phosphorothioic Acid The procedure of Example 1- is followed, using 9.0 parts of potassium 0,0-dimethyl phosphorothioate (0.05 mol) and 10.1 parts of 2-ibrornomethyl-4,6-dimcthyl-striazine'(0.0S mol) in 140 parts (by volume) of anhydrous acetone. The mixture is refluxed for one hour.

It is then cooled to room temperature and the solids are filtered off. The filtrate, after washing and evaporation, is recovered giving a colorless oil in 30% yield.

EXAMPLE 7 0,0,0',O'-Tetramethyl S,S'-(6-Methyl-s-Triazin-2,4-Diyldimethylene) Ester of. Phosphorodithioic Acid 3.77 parts of potassium 0,0-dimethyl phosphorodithioate (0.0192 mol) and 2.71 parts of 2,4-bis-(bromo- 5 methyl)-6-methyl-s-triazine (0.0096 mol) are dissolved in a total of 25 parts of anhydrous acetone. The mixture is heated at 50 C. for fifiteen minutes. it is then cooled to room temperature and the solids are filtered off. The filtrate is washed, dried and evaporated to yield 33% of theory of a colorless oil having a refractive index (n =1.5838.

EXAMPLE 8 O,S Dimethyl S (4,6 Dimethyl-s-Triazin-Z-Yl)M ethyl Ester of Phosphorodithioic Acid The procedure of Example 1 is repeated, using 9.8 parts of potassium O,S-dimethyl phosphorodithioate (0.05 mol) and 10.1 parts of 2-bromomethyl-4,6-dimethyl-s-triazine (0.05 mol) in 140 parts of anhydrous acetone. The mixture is heated to reflux for one and one-half hours and the desired product recovered as a light tan oil. Subsequent chromatographic purification gives a 25% yield of product as a light tan oil.

EXAMPLE 9 0,0-Dimethyl S-1-(s-Triazin-2-Yl)Ethyl Ester of Phs phorodithioic Acid In a suitable vessel are dissolved 9.8 pants of potassium 0,0-dimethyl phosphorodithioate (0.05 mol) and 7.8 parts of 2-(l-chloroethyD-s-triazine (0.05 mol) in 140 parts (by volume) of anhydrous acetone. The mixture is refluxed for eight and, one-half hours. Chroma tographic purification of resultant crude product yields the pure material as an oil having a refractive index (n ==1.5557.

EXAMPLE 10 0,0-Dimethyl S-(4,6-Dimthoxy-s-Triazin-2--Yl)Methyl Ester of Phosphorodithioic Acid The procedure of Example 1 is followed in everydetail, except that 2.75 parts of the potassium 0,0-dimethyl phosphorodithioate (0.014 mol) and 2.66 parts of 2-chloromethyl-4,6-dimethoxy-s-triazine (0.014 mol) in a total of 100 parts (by volume) of acetone are employed. After stirring at room temperature overnight, 98% of theory of potassium chloride are filtered ofi. Chromatographic purification of the crude product yields 50% of theory of the analytically pure product as a colorless oil with a refractive index (11 equal to 1.5486.

EXAMPLE 11 0,0 Dimelhyl S (4,6-Dithoxy-s-Triazin-Z-Yl)Methyl Ester of Ph osphorodithioic Acid TABLE 1 Percent Kill Aphids Example Product 1 (CHaOhE-SCHl O/Ha 100 100 100 N// E S N N l 2 (CzHxsO):I SCHz LN JCH: 100 100 49 t w N 3 (oH),P-scH-L )-ozm 100 s i e N 4 (CH3O)2PSCHLN/)CH3 .100 0 t N 5 (CHaO)zP-SCHILN J 100 100 '28 CHaO O N N \H II I 6 PSCHz-C C-CH; 100 50 (EH30 N TABLE I-Oontinued Percent Kill Aphids Example Product s i N N s 7 I! H 7 (CHaO)2P-SCHzlN CHzS-P (OCHQ: 100 8 e M t a s P-s-H -0\ 0-0H3 100 100 0113s N/ I i 7 CHaO S CH3 N "\N \H I II t 9 PSCHC CH 100 0 7 CHaO N I OCH3 0Hao\fi lTT 1o P-S;C'H3C C-OCH 100 1 100 we CH/ N (IMHE 01130 s \N \II II I 11 /PSCH2Q /CV.QO2H6 100 98 i We claim: I 2. 0,0-dimethy1 S44,6-dirnethyl-s-triazin-2-yl) methyl 1. A tnaziny-l alkyl phosphate ester of the formula: ester of phosphorodithioic acid. 7

I 3. 0,0-diethyl S-(4,6-dimethyl-s-tr-iazin-Z-yl) methyl ester of phosphorodithioic acid. 0 4 0,0-dimethyl S-l (4,6-diethyl-s-triazin-2-yl) ethyl R0 Y ester of phosphorodithioicacid.

\II I II 5. 0,0-di-methyl 8 1-(4,G-dimethyl-s-triazin-Z-yl) ethyl fi -FR f ester of phosphorodithioic acid. RY R N, 6. 0,0-dimethyl S-(s-triazin-Z-yDmethyl ester of phosphorodithioic acid. wherem R a are alkyl, :E R 7. 0,-O-dimetl1yl S- (4,G-di-methoXys-triaZin-Z-yI) methresent a radical selected from the group consisting of hyyl ester of phosphorodithioic acid. drogen and lower alkyl; Y and Y' represent an atom selects g f tgedgroup l i k 1 (fi i li lg B References Cited in the file of this patent s an s or y rogen, ower a y an ower a oxy, represents a radical selected from the group consisting of UNITE? STATES PATENTS hydrogen, lower alkyl, lower alk-oxy and the radical: 2,736,726 Gaetzl et a1 Feb. 28, 1956 25 880207 Schroeder et 'al Mar. 31, 1959 2,887,432 Baker et a1 M ay19, 11959 CSP Ra Y/R, FOREIGN PATENTS v 572,314 Belgium Apr. 23, 1959 wherein R, R, R R Y and Y' have the values as above 936,690 Germany Dec. '22, 1955 defined. a Canada Feb. 4, 1958 

1. A TRIAZINYL ALKYL PHOSPHATE ESTER OF THE FORMULA: 